Hydantoin acyl halides and their use as insecticides

ABSTRACT

ACYL HYDANTOIN DERIVATIVES DEFINED BY THE FOLLOWING STRUCTURAL FORMULA:   1-(X-C(-R6)(-R7)-CO-),2,5-DI(O=),3-R1,4-R2,4-R3-   IMIDAZOLIDINE   WHEREIN R1 IS ONE SELECTED FROM THE GROUP CONSISTING OF C1-C6 LOWER ALKYL OPTIONALLY SUBSTITUTED BY CHLORINE, BROMINE, C1-C6 ALKOXY AND C1-C6 ALKYLTHIO; C3-C6 ALKENYL; C3-C6 ALKYNYL; C3-C8 CYCLOAKLYL; OR PHENYL OPTIONALLY SUBSTITUTED WITH CHLORINE, BROMINE, TRIFLUROMETHYL OR NO2. R2 AND R3 CAN BE THE SAME OR DIFFERENT AND EITHER ONE IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, C1-C4 ALKYL, C1-C4 CHLOROALKYL, PHENYL OPTIONALLY SUBSTITUTED WITH CHLORINE OR NITRO AND C1-C4 ALKOXY. X IS ONE SELECTED FROM THE GROUP CONSISTING OF CHLORINE, BROMINE, FLUORINE AND A MOIETY DEFINED BY   -S-P(=Y)(-R3)-R5   HAVE BEEN FOUND TO POSSESS POST-EMERGENCE HERBICIDAL ACTIVITY. IN THIS STRUCTURE, R1, R2,R3, R7 AND R6 ARE DEFINED AS HEREINABOVE, AND Q IS ONE SELECTED FROM THE GROUP CONSISTING OF CHLORINE, BROMINE AND FLUORINE.   IMIDAZOLIDINE   1-(Q-C(-R6)(-R7)-CO-),2,5-DI(O=),3-R1,4-R2,4-R3-   WHEREIN Y CAN BE EITHER O OR S AND R4 AND R5 CAN BE THE SAME OR DIFFERENT AND SELECTED FROM THE GROUP CONSISTING OF C1-C6 ALKOXY, C1-C6 ALKYL, C1-C6 ALKYLTHIO, PHENYL OPTIONALLY SUBSTITUTED WITH CHLORINE OR BROMINE, PHENOXY OPTIONALLY SUBSTITUTED WITH CHLORINE OR BROMINE; R6 AND R7 CAN BE THE SAME OR DIFFERENT AND CAN BE SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, AND C1-C6 ALKYL. ORGANIC COMPOUNDS REPRESENTED BY THIS STRUCTURE HAVE BEEN FOUND TO HAVE PESTICIDAL, PARTICULARLY INSECTICIDAL, ACTIVITY. COMPOUNDS REPRESENTED BY THE FOLLOWING STRUCTUTE:

United States Patent 3,776,921 HYDANTOIN ACYL HALIDES AND THEIR USE AS INSECTICIDES Gophal H. Singhal, Westfield, N.J., and Joseph H. Lesser,

Woodside, N.Y., assignors to Esso Research and Engineering Company No Drawing. Original application Apr. 23, 1970, Ser. No. 31,405, now abandoned. Divided and this application Dec. 17, 1971, Ser. No. 209,449

Int. Cl. C0711 49/32; (307]? 9/08 U5. Cl. 260309.5 6 Claims ABSTRACT OF THE DISCLOSURE Acyl hydantoin derivatives defined by the following structural formula:

wherein R is one selected from the group consisting of C -C lower alkyl optionally substituted by chlorine, bromine, C -C alkoxy and C -C alkylthio; C -C alkenyl; C C alkynyl; C -C cycloalkyl; or phenyl optionally substituted with chlorine, bromine, trifluoromethyl or N0 R and R, can be the same or different and either one is selected from the group consisting of hydrogen, C -C alkyl, C -C chloroalkyl, phenyl optionally substituted with chlorine or nitro and C -C alkoxy. X is one selected from the group consisting of chlorine, bromine, fluorine and a moiety defined by have been found to possess post-emergence herbicidal activity. In this structure, R R R R and R are defined as hereinabove, and Q is one selected from the group consisting of chlorine, bromine and fluorine.

This is adivision of application Ser. No. 31,405 filed Apr. 23, 1970 now abandoned.

This invention relates to novel derivatives of hydantoins. In one aspect, this invention relates to the 1-acylphosphoryl derivative of hydantoins and their use as an insecti- 3,776,921 Patented Dec. 4, 1973 ice cide. In another aspect, this invention relates to the l-halo-acyl-hydantoin derivatives and their use as postemergence herbicides.

Acyl hydantoin derivatives of this invention are characterized by the following structural formula:

wherein R is one selected from the group consisting of C -C lower alkyl optionally substituted by chlorine, bromine, C -C alkoxy and C -C alkylthio; C -C alkenyl; C C alkynyl; C -C cycloalkyl; phenyl optionally substituted with chlorine, trifluoromethyl, bromine or N0 R and R can be the same or different and either one is selected from the group consisting of hydrogen, C -C alkyl, C -C chloroalkyl, phenyl optionally substituted by chlorine or nitro and C -C alkoxy. X is one selected from the group consisting of chlorine, bromine, fluorine and a group defined by f -S- I -R4 wherein Y can be either 0 or S and R and R can be the same or difierent and selected from the group consisting of C -C alkoxy, C -C alkyl, 8 -0 alkylthio, phenyl optionally substituted with chlorine or bromine, phenoxy, optionally substituted with chlorine or bromine, and R and R, can be the same or different and can be selected from the group consisting of hydrogen, and C -C alkyl.

The acyl hydantoin derivatives corresponding to the following structure:

wherein R R R R and R are as defined hereinabove and Q is either chlorine, bromine, or fluorine have been found to be effective herbicides.

Specific examples of compounds having the above compound structure are listed hereinbelow.

Compound No.:

1-3-chloroacetyI-Z-methylhydantoin 2-3-brornoacetyll-methylhydantoin 33-chloroacetyl-l-(p-chlorophenyl)-hydantoin 4-3 -chloro acetyl- 1- 3 ,4-dichlorophenyl) hydantoin 53-chloroacetyl-1-(2,4-dichlorophenyl)hydantoin 63-chloroacetyl-l-(2,4-dinitrophenyl)-hydantoin 73-chloroacetyl-l-nitro-hydantoin 83-chloroacetyl-allyl-hydantoin 9--3 -chloroacetyl-1- fl-methoxyethyl) -hydantoin 10-3 -bromoacetyl-l-nitro-hydantoin 1 13-chloroacetyl-1-trichloromethyl-hydantoin 12-3 2- chloropropionyl) -1-methyl-hydantoin 1 3-3- (2- chloro-Z-methyl-propionyl) l-methyl-hydantoin 143-chloroacetyl-1,5,5-trimethyl-hydantoin 3 Compound No.:

153-chloro acetyl-l-methyl-S,S-diphenyl-hydantoin l6--3-chloroacetyl-1-methyl-5-benzylidene-hydantoin 17S-[ l-rnethylhydantoinyl) -3 -acetyl] -0,0-dimethyl monothiophosphate 18S-[ l-methylhydantoinyl) -3-acetyl] -0,0-diethyl monothiophosphate 19S-[ l-methylhydantoinyl) -3-acetyl] -0,0-dimethyl dithiophosphate 20-S-[ l-methylhydantoiuyl -3-acetyl] -0,0-diethyl dithiophosphate 21S- l-methylhydantoinyl) -3-acetyl] -O-ethyl-s-npropyl dithiophosphate 22S-[ (1-methoxyethylhydantoinyl)-3-acetyl]-0,0-dimethyl monothiophosphate 23-$-[ l-allylhydontoinyl) -3-acetyl]-0,0-dimethyl monothiophosphate 24S-[ l-nitrohydantoinyl) -3-acetyl] -0,0-dimethyl monothiophosphate 25[ l-methylhydantoinyl) -3-acetyl] -0,0-dimethyl monothiophosphate The foregoing compounds can be readily prepared by the following method:

STEP I n, R. o Rim-4H2. Q-il-ii-Y Reactant A Reactant B wherein R R R R R and X are the same as defined hereinbefore and Y is either C1 or H OCCHzQ M is either K, Na or NH, and Y, R, and R are as de fined hereinabove.

This reaction can be carried out at temperatures ranging from 0l75 (3., preferably 25-80 C., under am bient pressure in the presence of a solvent selected from the group consisting of ether, acentonitrile, benzene, toluene at a mole ratio of C/D ranging from 1:1 to 1:20, preferably 1:1. The preferred solvent is acetonitrile.

The compounds of this invention have general pesticidal properties. They are useful as insecticides and, as stated hereinabove, the halogen derivatives have been found to have post-emergence herbicidal and insecticidal activity. 7

The compounds of the invention have general herbicidal and insecticidal properties. They are especially useful in certain types of weed control such as, for example, in application to crop lands to give control of the common weeds, without harming the crop plants; and for the control of crabgrass in lawns.

Herbicidal and insecticidal compositions of the invention are prepared by admixing one or more of the active ingredients defined heretofore, in herbicidally and insecticidally effective amounts with a conditioning agent of the kind used and referred to in the art as a pest control adjuvant or modifier to provide formulations adapted for ready and efiicient application to soil or Weeds (i.e., unwanted plants) or for overall pesticidal application using conventional applicator equipment.

Thus, the herbicidal and insecticidal compositions or formulations are prepared in the form of solids or liquids. Solid compositions are preferably in the form of granulars or dusts.

The compositions can be compounded to give homogeneous free-flowing dusts by admixing the active compound or compounds with finely divided solids preferably talc, natural clays, pyrophyllite, diatomaceous earth, or flours such as walnut shell, wheat, redwood, soya bean, and cottonseed flours. Other inert solid conditioning agents or carriers of the kind conventionally employed in preparing pest control compositions in powdered form can be used.

Granulars can be compounded by absorbing the compound in liquid form onto a preformed granular diluent. Such diluents as natural clays, pyrophyllite, diatomaceous earth, flours such as walnut shell, as well as granular sand can be employed.

In addition, granulars can also be compounded by admixing the active ingredient with one of the powdered diluents described hereinabove, followed by the step of either pelleting or extruding the mixture.

Liquid compositions of the invention are prepared in the usual way by admixing one or more of the active ingredients with a suitable liquid diluent medium. In the cases where the compounds are liquids, they may be sprayed in ultra low volume as such. With certain solvents, such as alkylated naphthalene or other aromatic petroleum solvents, dimethyl formamide, cycloketone, relatively high up to about 50% by weight or more concentration of the active ingredient can be obtained in solution.

The herbicidal and insecticidal compositions of the invention whether in the form of dusts or liquids, preferably also include a surface-active agent sometimes referred to in the art as a wetting, dispersing, or emulsifying agent. These agents, which will be referred to hereinafter more simply as surface-active dispersing agents, cause the compositions to be easily dispersed in water to give aqueous sprays which, for the most part, constitute a desirable composition for application.

The surface-active dispersing agents employed can be of the anionic, cationic, or nonionic type and include, for example, sodium and potassium oleate, the amine salts of oleic' acid, such as morpholine and dimethylamine oleates,

, the sulfonated animal and vegetable oils, such as sulfonated fish castor oils, sulfonated petroleum oils, sulfonated acyclic hydrocarbons, sodium salt of lignin sulfomc acid (gaulac), alkylnaphthalene sodium sulfonate, sodium salts of sulfonated condensation products of naphv thalene and formaldehyde, sodium lauryl sulfate, disodium monolauryl phosphate, sorbitol laurate, pentaerythritol monostearate, glycerol monostearate, diglycol oleate, polyethylene oxides, ethylene oxide condensation products with stearyl alcohol and alkylphenol, polyvinyl alcohols, salts, such as the acetate of polyamines from reductive amine.- tion of ethylene/carbon monoxide polymers, laurylamine hydrochloride, laurylpyridinium bromide, stearyl trimethylammonium bromide, cetyldimethylbenzyl ammonium chloride, lauryldimethylamine oxide, and the like. Generally, the surface-active agent will not comprise more than about 5 to by weight of the composition, and in certain compositions the percentage will be 1% or less. Usually, the minimum lower concentration will be 0.1%.

The herbicidal and insecticidal compositions are applied either as a spray, granular or a dust to the locus or area to be protected from undesirable plant growth, commonly called weeds, i.e. plants growing where they are not wanted. Such application can be made directly upon the locus or area and the weeds thereon during the period of weed infestation in order to destroy the weeds, but preferably, the application is made in advance of an anticipated weed infestation to prevent such infestation. Thus, the compositions can be applied as aqueous foliar sprays but can also be applied as sprays directly to the surface of the soil. Alternatively, the dry powdered compositions can be dusted directly on the plants or on the soil.

In applying the herbicidal and insecticidal compositions of the invention for selective Weed control as in the control of weeds in cotton or cornfields, the compositions are preferably applied after planting of the crop seeds but before emergence of the seedlings. In other words, the applications are of the pre-emergence type.

The active compound is. of course, applied in an amount sufficient to exert the desired herbicidal action. The amount of the active compound present in the compositions as actually applied for destroying or preventing weeds will vary with the manner of application, the particular weeds for which control is sought, the purpose for which the application is being made, and like variables. In general, the herbicidal and insecticidal compositions as ap plied in the form of a spray, dust or granular, will contain from about 0.1% to 100% by weight of the active compound.

Fertilizer materials, other herbicidal agents, and other pest control agents such as insecticides and fungicides can be included in the herbicidal and insecticidal compositions of the invention if desired.

The term carrier or diluent as used herein means a material, which can be inorganic or organic and synthetic or of natural origin, with which the active ingredient is mixed or formulated to facilitate its storage, transport, and handling and application to the plants to be treated. The carrier is preferably biologically and chemically inert and, as used, can be a solid or fluid. When solid carriers are used, they are preferably particulate, granular, or pelleted; however, other shapes and sizes of solid carrier can be employed as well. Such preferable solid carriers can be natural occurring minerals-although subsequently subjected to grinding, sieving, purification, and/or other treatmentsincluding, for example, gypsum; tripolite; diatomaceous earth; mineral silicates such as mica, vermiculite, talc, and pyrophyllite; clays of the montmorillonite, kaolinite, or attapulgite groups; calcium or magnesium limes, or calcite and dolomite; etc. Carriers produced synthetical- 1y, as for example, synthetic hydrated silica oxides and synthetic calcium silicates can alsobe used, and many proprietary products of this type are available commercially. The carrier can also be an elemental substance such as sulfur or carbon, preferably an activated carbon. If the carrier possesses intrinsic catalytic activity such that it would decompose the active ingredient, it is advantageous to, incorporate a-stabilizing agent, as for example, polyglycols such as diethylene glycol, to neutralize this activity and thereby prevent possible decomposition of the derivatives of the present nitrated aryl compounds.

For some purposes, 'a resinous or waxy carrier can be used, preferably. one which is solvent soluble or thermoplastic, including fusible materials. Examples of such carriers are natural or synthetic resins such as a coumarone resin, rosin, copal, shellac, dammar, polyvinyl chloride, styrene polymers and copolymers, a solid grade of polychlorophenol such as is available under the registered trademark Arcolor, a bitumen, an asphaltite, a wax for example, beeswax or a mineral wax such as paraflin wax or montan wax, or a chlorinated mineral wax, or a microcrystalline wax such as those available under the registered trademark Mikrovan Wax. Compositions comprising such resinous or waxy carriers are preferably in granular or pelleted form.

Fluid carriers can be liquids, as for example, water, or an organic fluid, including a liquefied normally vaporous or gaseous material, or a vaporous or gaseous material, and can be solvents or nonsolvents for the active material. For example, the horticultural petroleum spray oils boiling in the range of from about 275 to about 575 F., or boiling in the range of about 575 to about 1,000 F. and having an unsulfonatable residue of at least about 75% and preferably of at least about 90%, or mixtures of these two types of oil, are particularly suitable liquid carriers.

The carrier can be mixed or formulated with the active material during its manufacture or at any stage subsequently. The carrier can be mixed or formulated with the active material in any proportion depending on the nature of the carrier. One or more carriers, moreover, can be used in combination.

The compositions of this invention can be concentrates, suitable for storage or transport and containing, for example, from about 5 to about 90% by weight of the active ingredient, preferably from about 20 to about wt. percent. These concentrates can be diluted with the same or different carrier to a concentration suitable for application. The compositions of this invention may also be dilute compositions suitable for application. In general, concentrations of about 0.1 to about 10% by weight, of active material based on the total weight of the composition are satisfactory, although lower and higher concentrations can be applied if necessary.

The compositions of this invention can also be formulated as dusts. These comprise an intimate admixture of the active ingredient and a finely powdered solid carrier such as aforedescribed. The powdered carriers can be oil-treated to improve adhesion to the surface to which they are applied. These dusts can be concentrates, in which case a highly sorptive carrier is preferably used. These require dilution with the same or a different finely powdered carrier, which can be of lower sorptive capacity, to a concentration suitable for application.

The compositions of the invention can be formulated as wettable powders comprising a major proportion of the active ingredient mixed with a dispersing, i.e. deflocculating or suspending agent, and if desired, a finely divided solid carrier and/or a wetting agent. The active ingredient can be in particulate form or adsorbed on the carrier and preferably constitutes at least about 10%, more preferably at least about 25%, by Weight of the composition. The concentration of the dispersing agent should in general be between about 0.5 and about 5% by weight of the total composition, although larger or smaller amounts can be used if desired.

The dispersing agent used in the composition of this invention can be any substance having definite dispersing, i.e., deflocculating or suspending, properties as distinct from wetting properties, although these substances can also possess wetting properties as well.

The dispersant or dispersing agent used can be protective colloids such as gelatin, glue, casein, gums, or a synthetic polymeric material such as polyvinyl alcohol and methylcellulose. Preferably, however, the dispersants or dispersing'agents used are sodium or calcium salts of high molecular weight sulfonic acids, as for example, the sodium or calcium salts of lignin sulfonic acids derived from sulfite cellulose waste liquors. The calcium or sodium salts of condensed aryl sulfonic acid, for example, the products known as Tamol 731, are also suitable.

The wetting agents used can be nonionic type surfactants, as for example, the condensation products of fatty acids containing at least 12, preferably 16 to 20, carbon atoms in the molecule, or abietic acid or naphthenic acid obtained in the refining of petroleum lubricating oil fractions with alkylene oxides such as ethylene oxide or propylene oxide, or with both ethylene oxide and propylene oxide, as for example, the condensation product of oleic acid and ethylene oxide containing about 6 to 15 ethylene oxide units in the molecule. Other nonionic wetting agents like polyalkylene oxide polymers, commercially known as Pluronics can be used. Partial esters of the above acids with polyhydric alcohols such as glycerol, polyglycerol, sorbitol, or mannitol can also be used.

Suitable anionic wetting agents include the alkali metal salts, preferably sodium salts, of sulfuric acid esters or sulfonic acids containing at least 10 carbon atoms in a molecule, for example, the sodium secondary alkyl sulfates, dialkyl sodium sulfosuccinate available under the registered trademark Teepol, sodium salts of sulfonated castor oil, sodium dodecyl benzene sulfonate.

Granulated or pelleted compositions comprising a suitable carrier having the active ingredient incorporated therein are also included in this invention. These can be prepared by impregnating a granular carrier with a solution of the inert ingredient or by granulating a mixture of a finely divided solid carrier and the active ingredient. The carrier used can consist of or contain a fertilizer or fertilizer mixture, as for example, a superphosphate.

The compositions of this invention can also be formulated as solutions of the active ingredient in an organic solvent or mixture of solvents, such as for example, alcohols; ketones, especially acetone; ethers; hydrocarbons; etc.

Where the toxicant itself is a liquid these materials can be sprayed on crops or insects without further dilution.

Petroleum hydrocarbon fractions used as solvents should preferably have a flash point above 73 F., an example of this being a refined aromatic extract of kerosene. Auxiliary solvents such as alcohols, ketones, and polyalkylene glycol ethers and esters can be used in conjunction with these petroleum solvents.

Compositions of the present invention can also be formulated as emulsifiable concentrates which are concentrated solutions or dispersion of the active ingredient in an organic liquid, preferably a water-insoluble organic liquid, containing an added emulsifying agent. These concentrates can also contain a proportion of water, for example, up to about 50% by volume, based on the total composition, to facilitate subsequent dilution with water. Suitable organic liquids include, e.g., the above petroleum hydrocarbon fractions previously described.

The emulsifying agent can be of the type producing water-in-oil type emulsions which are suitable for application by low volume spraying, or an emulsifier of the type producing oil-in-water emulsions can be used, producing concentrates which can be diluted with relatively large volumes of water for application by high volume spraying or relatively small volumes of water for low volume spraying. In such emulsions, the active ingredient is preferably in a nonaqueous phase.

The present invention is further illustrated in greater detail by the following examples, but it is to be understood that the present invention in its broadest aspects, is

not necessarily limited in terms of the reactants, or specific 7 8 EXAMPLE 1 Preparation of 3-chloroacetyl-l-methylhydantoin A mixture of 46 g. (0.4 M) of l-methyl hydantoin, 88 g. (0.8 M) chloroacetyl chloride, and 200 ml. of toluene were refluxed for 6 hrs. The volatiles were removed under reduced pressure leaving the crude product as a brown crystalline solid, wt. 68.6 g.

A sample was recrystallized from ether/ methylene chloride for elemental analyses, M.P. 7273.

Found (percent): C, 38.14; H, 3.84; N, 14.77. Calculated (percent): C, 37.80; H, 3.70; N, 14.70.

EXAMPLE 2 Preparation of 1-t-butyl-3-chloroacetyl hydantoin A mixture of 40.0 g. (0.26 M.) of l-t-butyl hydantoin 66 g. (0.6 M) of chloroacetylchloride, and 250 ml. of toluene were refluxed for 4 hours. The clear brown reaction solution was then stripped, leaving 49 g. of brown crystalline solid.

An analytical sample was prepared by recrystallization from ether, M.P. 103-1045.

Analysis-Found (percent): C, 46.41; H, 5.60; N, 11.96. Calculated (percent): C, 48.53; H, 5.88; N, 12.50.

EXAMPLE 3 'Preparation of 1-allyl-3-chloroacetyl hydantoin A mixture of 70 g. (0.5 M) of l-allyl hydantoin, 100 g. of chloroacetyl chloride, and 250 ml. of toluene were refluxed for 4 hours. The cool, pale yellow reaction solution contained a precipitate which was filtered, wt. 30.0g., M.P. 84-6. The remaining product was obtained by removing the volatiles under reduced pressure from the filtrate. This gave an additional 70.0 g. of product.

The structure was confirmed by NMR analysis.

EXAMPLE 4 Preparation of 3-chloroacetyl-1- (fl-methoxyethyl) hydantoin A mixture of g. (0.5 M) of l-fi-methoxyethyl hydantoin and g. of chloroacetyl chloride were refluxed in 250 ml. of toluene for 4 hours. From the clear brown reaction solution, volatiles were removed under reduced pressure to give 115.4 g. of brown crystalline solid.

The solid was shown to be about 75% pure product by NMR analysis.

EXAMPLE 5 Preparation of S- 1-methy1hydantoinyl-3 -acyl] phosphorothioate H! s P (0 Q1115):

A mixture of 19.0 g. (0.1 M) of 1-methyl-3-chloroacetyl hydantoin, 19.0 g. (0.1 M) of S-ammonium-0,0'-diethoxy phosphorothioate, and ml. of acetonitrile was refluxed for 1.5 hrs. The reaction mixture was filtered, stripped on a rotary evaporator (15 mm. Hg/40), and the residue dissolved in 150 ml. of chloroform. The chloroform solution was washed with 50 ml. of cold water twice, tyvice with 50 ml. of 5% aqueous bicarbonate solution, and dried over anhydrous sodium sulfate. The chloroform solution was 0 filtered and the volatiles removed on a rotary evaporator at 15 mm./50 and then under high vacuum (0.1 mm.) at 50 for 48 hrs.

The resulting clear brown oil was shown by NMR spectroscopy and elemental analysis, to be the desired phosphate, wt. 11.6 g.

Elemental wnalysis.-Calculated (percent): C, 37.03; H, 5.28; N, 9.55. Found (percent): C, 35.94; H, 5.50; N, 9.78. I

EXAMPLE 6 Preparation of S-( 1-methy1-3-hydantoinylacetyl)-0,0-

diethoxy phosphorodithioate CHQN A mixture of 10 g. (0.05 M) of 3-chloroacetyl-1-methyl TABLE I.HYDANTOINYL PHOSPHOROUS ESTERS Analysis (percent) Found Calculated Compound 0 H N P C H N P R =CHa S(nC:H 3704 5.50765 37.28 5.40 7.90 8.74 R2=(J CH2 s 1|*\ 0 OCgHs R'ICH:

H H Structure confirmed by NMR R =(CHa0)zP s 01120- 12 =(02Hto)ifiscm(fi- 41.72 6.22 8.19 40.91 6.01 7.95

R"=(CHa)aCH RI=(CQH5O)BPSCHZC 36.63 5.82 7.67 39.12 5.74 7.60 8.40

R"'=(CH3):CH

R =(CHa)aC Structure confirmed by NMR B =(CHaO)z1lT s 011200 hydantoin, g. (0.05 M) S-ammonium-0,0-diethoxy EXAMPLE 8 phosphorodithioate, and 100 ml. of acetonitrile were re- Re resentafive derivatives of the haloae Iated h fluxed for 2 hrs. The reaction mixture was allowed to cool 55 g compounds of this invention were evgluated 3 to room temperature; filtered Stripped. on rqtary evap' post-emergence activity. The test procedure was as orator (50/ mm. Hg), and then dissolved in 150 ml. follows: chloroform. The chloroform solution was washed with Two flats containing Six Weeds Whose first true leaves 5% aqueous blcflrbonate, of Saturated Nacl have appeared were sprayed at a rate of 10 lb./a. The solution, and then dned over SOdllllTl sulfate (anhydrous). flats were then held in the greenhouse and the response The chloroform solution was filtered and the volatiles re rated ft 124 days Response is rated on a 1 1O moved on a rotary evaporator first at 15 mm. Hg/ 50 and scale were 1: i j nd 10=comp1ete kill. then for 18 500/01 The resldue was Herbieidal testing of 1-methyl-3-ch1oroacetylhydantoin (post emerclear pale brown 011, wt. 14.4 g. gence) The structure of the product was confirmed by NMR Weeds and elemental analysis.

MG CG BG F Zi M Elemental analysis.--Calculated (percent): C, 35.29; x u H, 5,03; N, 8.23. Found (percent): C, 35.42; H, 5.17; N, cwcentmwn 1o lbs'la 7 9 9 10 N .Wh :MG=M 1 ;CG=C b ;BG=B 8'08 yarrfgass;Ff lii hxtail;zi= i n ri ag fi u =Mustard grass am EXAMPLE 7 EXAMPLE 9 Representative acylhydantoin derivations from those A number of Phosphoric and thiOPhQSPhOTIC 301d esters prepared in the previous examples were evaluated for of 1-substituted hydantoins and 3-substituted hydantoins their insecticidal activity.

The experimental compounds were tested as aqueous emulsions. These emulsions were prepared by dissolving the compound in acetone and dispersing it in distilled water with Triton X-100 an alkylaryl polyether alcohol derived by the reaction of l-octylphenol with ethylene oxide to give spray emulsions containing the desired concentration of the compound. These emulsions were then used in standard laboratory tests described below.

Mexican bean beetle Bean leaves were dipped in the emulsion of the test chemical and allowed to dry. The individually treated leaves were placed in Petri dishes and five Mexican bean beetle larvae introduced into each of the two replicate dishes.

Mite contact Potted bean plants infested with two spotted spidermites were placed on a turntable and sprayed with a formulation of the test chemical. The plants were held for 7 days and the degree of mite control was rated after this period.

Mites systemic Bean plants were treated by applying 20 milliliters of the formulated test chemical to the soil. The mites were transferred to the plants after 24 hours. The plants were held for 7 more days and the degree of mite control rated.

12 Aphid contact Potted nasturtium plants infested with the bean aphids were placed on a turntable and sprayed with a formulation of the test chemical. The plants were held for two days and the degree of aphid control was rated.

Aphid systemic Nasturtium plants are treated by applying 20 milliliters of the formulated test chemical to the soil. The mites were transferred to the plant after 24 hours. The plants were held for 48 additional hours and the degree of the aphid control rated.

Boll weevil Five mixed sex adult boll weevils placed in a wire screen cage were sprayed with the proper concentration of formulated test chemical. The boll weevils were provided with succrose solution on a filter paper. The cages were held at about F. for 24 hours and the percent mortality read after 24 hours.

The compounds were also tested against Southern Army Worm (class Lepidoptera), other insects of aphid (Order- Homoplera), other members of the Coleopterous order, such as confused flour beetle and spider beetle, and against resistant mites and were found to be active. The results of the insecticidal evaluations are given in Table H.

TABLE IL-INSECTICIDAL ACTHggY 0F HYDANIOIN-B-AND -l-ACYL PHOSPHORIC ID ESTER DERIVATIVES Mortality (percent) at 250 ppm.

Mites 1 Contact Systemic Bean aphids C om Compound MBB 1 Adults Nymphs Adults Nymphs Contact Systemic rootworm R =CH3 R=CO oms w cam), 100 90 80 80 0 R CH:

m=oocms1r oomn 100 100 90 100 100 90 90 80 R CH:

R =C0CHS1||(OCH5)| 0 100 90 100 100 I 0 20 0 R =CH;

S (nC H 0 0 0 0 0 0 0 0 R==C 0 CH: S P

ll 0 0 C111;

R =C0CH;S1||(OC;H;): 100 100 100 10 0 10 40 60 R CH(CH3):

R =COCHlSP(OC;H 100 0 0 0 0 0 0 80 1 MBB=Mexican bean beetle. I Mltes=2 spotted spider mites. Corn rootworm run at 2.5 p.p.m.-

13 14 What is claimed is: References Cited 1. A compound Of the formula ST P Pfl-Nficlh 3,406,179 10/1968 Jamison 260-3097 3,687,966 8/1972 Haubein 260309.5

it FOREIGN PATENTS 6900039 7/1969 Netherlands 260309.5

OTHER REFERENCES wherein R is alkyl of from 1 to 6 carbon atoms optionally substituted by methoxy, allyl or dichlorophenyl; 10 3;? et chem Abst" column 12894 and Q is chlorine or bromine. z. A compound according to claim 1, 3 ch1oroacety1 Mlfilgegggura et al.. Chem. Abst., vol. 63, columns 16973 l-methyl hydantoin.

3. A compound according to claim 1, (lggglmatsu et al.. Chem. Abst., vol. 62, column 7768 chloroacetyl-hydantoin.

4. A compound according to claim 1, y Umemoto. Chem. Abst., vol. 61, column 8296 (1964).

acetyl-hydantoin. NATALIE TROUSOF P E 5. A compound according to claim 1, 3-chloroacety1- nmary xammer l-fl-methoxyethyl-hydantoin. US. Cl, X.R.

6. A compound according to claim 1, 3-chloroacety1- 1-(2,4-dichloropheny1) hydantoin. 71-92; 273 

